Abstract: Total reflection X-ray fluorescence (TXRF) spectroscopy is an X-ray analytical technique different from conventional X-ray fluorescence spectroscopy (XRF), mainly used for chemical analysis of trace samples and trace elements, and has been widely used in the field of environmental science. Sample pretreatment is an essential step in the analysis and measurement process. It is necessary to select an appropriate pretreatment method according to the nature of the sample to be tested. The quality of the sample pretreatment process plays a decisive role in the measurement results. In this paper, the development history of TXRF analysis technology is reviewed, its principles and characteristics are briefly introduced, and the sample pretreatment methods of TXRF analysis technology and their applications in environmental science are summarized in focus.